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US5373080A - Process for producing polycarbodiimide resin - Google Patents

Process for producing polycarbodiimide resin Download PDF

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Publication number
US5373080A
US5373080A US08/101,309 US10130993A US5373080A US 5373080 A US5373080 A US 5373080A US 10130993 A US10130993 A US 10130993A US 5373080 A US5373080 A US 5373080A
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United States
Prior art keywords
phospholene
polycarbodiimide resin
oxide
resin
methyl
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Expired - Lifetime
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US08/101,309
Inventor
Yasuo Imashiro
Ikuo Takahashi
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Nisshinbo Holdings Inc
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Nisshinbo Industries Inc
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Assigned to NISSHINBO INDUSTRIES, INC. reassignment NISSHINBO INDUSTRIES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMASHIRO, YASUO, TAKAHASHI, IKUO
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring

Definitions

  • the present invention relates to a process for producing a polycarbodiimide resin. More particularly, the present invention relates to a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
  • Polycarbodiimide resins having a structure of --N ⁇ C ⁇ N-- in the molecule are known to have high heat resistance and other excellent properties and are in use in various fields as a thermosetting resin.
  • Polycarbodiimide resins have been produced in a reaction system using a solvent, except for few exceptional cases, because since the reactivity of carbodiimide group is high, carbodiimidization in high degree invites gelling due to the occurrence of side reactions. Consequently, the resulting polycarbodiimide resin has had limited applications owing to the solvent used.
  • a polycarbodiimide resin produced using a high-boiling solvent finds no applications where a low-boiling solvent must be used.
  • the above polycarbodiimide resin may be used in said applications by conducting concentration to remove part or all of the high-boiling solvent and replace it with a low-boiling solvent.
  • concentration to remove part or all of the high-boiling solvent and replace it with a low-boiling solvent.
  • carbodiimide group since the reactivity of carbodiimide group is so high as to invite gelling even in a solution, it is virtually very difficult to remove part or all of the high-boiling solvent.
  • the present invention has been brought about in order to eliminate the above drawbacks of the prior art and provide a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
  • a process for producing a polycarbodiimide resin from an aliphatic diisocyanate and a terminal-blocking agent in the presence of a carbodiimidization catalyst wherein the aliphatic diisocyanate is tetramethylxylylene diisocyanate represented by the following formula ##STR2## and polymerization is conducted using no solvent.
  • the aliphatic diisocyanate used in the present invention is tetramethylxylylene diisocyanate represented by the above formula. More specifically, it is exemplified by p-tetramethylxylylene diisocyanate represented by the following formula ##STR3## or m-tetramethylxylylene diisocyanate represented by the following formula.
  • the first feature of the present invention lies in that a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents is produced by using tetramethylxylylene diisocyanate.
  • the terminal-blocking agent used in the present invention includes, for example, an aliphatic monoisocyanate. It can be exemplified by n-butyl isocyanate, tert-butyl isocyanate, isobutyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, cyclohexyl isocyanate and n-octadecyl isocyanate. Of these, n-butyl isocyanate is particularly preferable.
  • tetramethylxylylene diisocyanate and the terminal-blocking agent are subjected to a condensation reaction (wherein removal of carbon dioxide takes place) to produce a polycarbodiimide resin.
  • the basic reaction is the same as in the conventional processes for polycarbodiimide resin production [U.S. Pat. No. 2,941,956; Japanese Patent Publication No. 33279/1972; J. Org. Chem., 28,2069-2075 (1963); Chemical Review 1981, vol. 81, No. 4, 619-621].
  • the condensation reaction between tetramethylxylylene diisocyanate and an aliphatic monoisocyanate as terminal-blocking agent proceeds in the presence of a carbodiimidization catalyst.
  • a carbodiimidization catalyst there can be used, for example, phospholeneoxides such as 1-phenyl-2-phospholene-1-oxide, 3- methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2- phospholene1-oxide, 1-ethyl-2-phospholene1-oxide, 3methyl-1-phenyl-2-phospholene-1-oxide and 3-phospholene isomers thereof.
  • 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable in view of the reactivity.
  • an organic solvent has ordinarily been used in the conventional processes for aliphatic polycarbodiimide resin production. In the condensation reaction of the present process, however, no solvent is used, and this is a second feature of the present invention.
  • the temperature of the above condensation reaction is in the range of preferably about 120° C. to about 250° C., more preferably about 150° C. to about 190° C.
  • the amount ratio of tetramethylxylylene diisocyanate to the aliphatic monoisocyanate is preferably in the range of 2:1 to 2:30 (molar ratio). Consequently, the polymerization degree of the resulting polycarbodiimide resin becomes 1 to 30.
  • reaction between tetramethylxylylene diisocyanate and the aliphatic monoisocyanate as terminal-blocking agent is conducted in an inert gas (e.g. nitrogen) current to complete the reaction quickly.
  • an inert gas e.g. nitrogen
  • the polycarbodiimide resin obtained in the present process using no solvent is a viscous liquid resin and has no problem of limited applications seen in polycarbodiimide resins produced by the conventional processes using a solvent. Further, the polycarbodiimide resin obtained in the present process not only has very good storage stability but also is soluble in various organic solvents and can be used in various applications (e.g. crosslinking agent for aqueous resin) by selecting an appropriate solvent suitable for each application.
  • polycarbodiimide resins obtained in Examples 2-7 similarly to the polycarbodiimide resin obtained in Example 1, were soluble in various organic solvents.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a process for producing a polycarbodiimide resin from an aliphatic diisocyanate and a terminal-blocking agent in the presence of a carbodiimidization catalyst, wherein the aliphatic diisocyanate is tetramethylxylylene diisocyanate represented by the following formula ##STR1## and polymerization is conducted using no solvent. The polycarbodiimide resin obtained by the above process has good storage stability and excellent miscibility with organic solvents.

Description

BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to a process for producing a polycarbodiimide resin. More particularly, the present invention relates to a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
(2) Description of the Prior Art
Polycarbodiimide resins having a structure of --N═C═N-- in the molecule are known to have high heat resistance and other excellent properties and are in use in various fields as a thermosetting resin.
Polycarbodiimide resins have been produced in a reaction system using a solvent, except for few exceptional cases, because since the reactivity of carbodiimide group is high, carbodiimidization in high degree invites gelling due to the occurrence of side reactions. Consequently, the resulting polycarbodiimide resin has had limited applications owing to the solvent used.
For example, a polycarbodiimide resin produced using a high-boiling solvent finds no applications where a low-boiling solvent must be used.
The above polycarbodiimide resin may be used in said applications by conducting concentration to remove part or all of the high-boiling solvent and replace it with a low-boiling solvent. However, since the reactivity of carbodiimide group is so high as to invite gelling even in a solution, it is virtually very difficult to remove part or all of the high-boiling solvent.
Even if the above problem caused by the use of a solvent in polycarbodiimide production could be solved, problems still exist when the produced polycarbodiimide resin has low storage stability or poor miscibility with organic solvents.
SUMMARY OF THE INVENTION
The present invention has been brought about in order to eliminate the above drawbacks of the prior art and provide a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
According to the present invention there is provided a process for producing a polycarbodiimide resin from an aliphatic diisocyanate and a terminal-blocking agent in the presence of a carbodiimidization catalyst, wherein the aliphatic diisocyanate is tetramethylxylylene diisocyanate represented by the following formula ##STR2## and polymerization is conducted using no solvent.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is hereinafter described in detail.
The aliphatic diisocyanate used in the present invention is tetramethylxylylene diisocyanate represented by the above formula. More specifically, it is exemplified by p-tetramethylxylylene diisocyanate represented by the following formula ##STR3## or m-tetramethylxylylene diisocyanate represented by the following formula.
In the present invention, no other aliphatic diisocyanate can be used. That is, the first feature of the present invention lies in that a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents is produced by using tetramethylxylylene diisocyanate.
The terminal-blocking agent used in the present invention includes, for example, an aliphatic monoisocyanate. It can be exemplified by n-butyl isocyanate, tert-butyl isocyanate, isobutyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, cyclohexyl isocyanate and n-octadecyl isocyanate. Of these, n-butyl isocyanate is particularly preferable.
In the present process, tetramethylxylylene diisocyanate and the terminal-blocking agent are subjected to a condensation reaction (wherein removal of carbon dioxide takes place) to produce a polycarbodiimide resin. The basic reaction is the same as in the conventional processes for polycarbodiimide resin production [U.S. Pat. No. 2,941,956; Japanese Patent Publication No. 33279/1972; J. Org. Chem., 28,2069-2075 (1963); Chemical Review 1981, vol. 81, No. 4, 619-621].
The condensation reaction between tetramethylxylylene diisocyanate and an aliphatic monoisocyanate as terminal-blocking agent (wherein removal of carbon dioxide takes place) proceeds in the presence of a carbodiimidization catalyst. As said catalyst, there can be used, for example, phospholeneoxides such as 1-phenyl-2-phospholene-1-oxide, 3- methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2- phospholene1-oxide, 1-ethyl-2-phospholene1-oxide, 3methyl-1-phenyl-2-phospholene-1-oxide and 3-phospholene isomers thereof. 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable in view of the reactivity.
As mentioned above, an organic solvent has ordinarily been used in the conventional processes for aliphatic polycarbodiimide resin production. In the condensation reaction of the present process, however, no solvent is used, and this is a second feature of the present invention.
The temperature of the above condensation reaction is in the range of preferably about 120° C. to about 250° C., more preferably about 150° C. to about 190° C.
The amount ratio of tetramethylxylylene diisocyanate to the aliphatic monoisocyanate (terminal-blocking agent) is preferably in the range of 2:1 to 2:30 (molar ratio). Consequently, the polymerization degree of the resulting polycarbodiimide resin becomes 1 to 30.
The reaction between tetramethylxylylene diisocyanate and the aliphatic monoisocyanate as terminal-blocking agent is conducted in an inert gas (e.g. nitrogen) current to complete the reaction quickly.
The polycarbodiimide resin obtained in the present process using no solvent is a viscous liquid resin and has no problem of limited applications seen in polycarbodiimide resins produced by the conventional processes using a solvent. Further, the polycarbodiimide resin obtained in the present process not only has very good storage stability but also is soluble in various organic solvents and can be used in various applications (e.g. crosslinking agent for aqueous resin) by selecting an appropriate solvent suitable for each application.
The present invention is hereinafter described in more detail by way of Examples.
EXAMPLE 1
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 66 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
The solubility of the polycarbodiimide resin in various organic solvents is shown in Table 1.
              TABLE 1                                                     
______________________________________                                    
Solvent                  Solubility                                       
______________________________________                                    
Benzene                  Yes                                              
Toluene                  Yes                                              
Xylene                   Yes                                              
Acetone                  Yes                                              
Methyl ethyl ketone      Yes                                              
Ethyl acetate            Yes                                              
Amyl acetate             Yes                                              
Propylene glycol monomethyl ether acetate                                 
                         Yes                                              
Chloroform               Yes                                              
Carbon tetrachloride     Yes                                              
Methylene chloride       Yes                                              
Trichloroethylene        Yes                                              
Tetrachloroethylene      Yes                                              
Dimethylformamide        Yes                                              
______________________________________
EXAMPLE 2
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 150° C. for 100 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 3
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 170° C. for 103 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 4
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-l-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 190° C. for 77 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 5
244 g of m-tetramethylxylylene diisocyanate and 66 g of butyl isocyanate were reacted in the presence of 6.2 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 28 hours to obtain a polycarbodiimide resin (polymerization degree=3). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 6
244 g of m-tetramethylxylylene diisocyanate and 10.4g of butyl isocyanate were reacted in the presence of 5.1 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 126 hours to obtain a polycarbodiimide resin (polymerization degree=19). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 7
244 g of m-tetramethylxylylene diisocyanate and 6.83g of butyl isocyanate were reacted in the presence of 5.0 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 134 hours to obtain a polycarbodiimide resin (polymerization degree =29). The resin had a stability of more than one month at room temperature, which was excellent.
The polycarbodiimide resins obtained in Examples 2-7, similarly to the polycarbodiimide resin obtained in Example 1, were soluble in various organic solvents.
COMPARATIVE EXAMPLE 1
193.5 g of 4,4'-dicyclohexylmethane diisocyanate and 16.5 g of butyl isocyanate were reacted in the presence of 2.10 g of a carbodiimidization catalyst (3-methyl-1-phenyl2-phospholene-1-oxide) in a nitrogen gas current at 180° C. Gelling occurred in 10 hours and no polycarbodiimide resin was obtained.
COMPARATIVE EXAMPLE 2
181.6 g of isophorone diisocyanate and 18 g of butyl isocyanate were reacted in the presence of 2.0 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. Gelling occurred in 3 hours and no polycarbodiimide resin was obtained.

Claims (2)

What is claimed is:
1. A process for producing a polycarbodiimide resin comprising reacting a tetramethylxylylene diisocyanate represented by the following formula ##STR4## with an aliphatic monoisocyanate at a molar ratio of the tetramethylxylylene diisocyanate to the aliphatic monoisocyanate of 2:1 to 2:30 in the presence of a carbodiimidization catalyst selected from the group consisting of phospholeneoxides at a temperature in the range of about 120° C. to about 250° C. and in the absence of a solvent.
2. The process of claim 1, wherein the carbodiimidization catalyst is selected from the group consisting of 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.
US08/101,309 1992-08-10 1993-08-03 Process for producing polycarbodiimide resin Expired - Lifetime US5373080A (en)

Applications Claiming Priority (2)

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JP23533192A JP3188959B2 (en) 1992-08-10 1992-08-10 Method for producing polycarbodiimide resin
JP4-235331 1992-08-10

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EP0780440A2 (en) 1995-12-22 1997-06-25 Rohm And Haas Company Crosslinkable compositions with an aliphatil polycarbodiimide
US5688875A (en) * 1994-06-10 1997-11-18 Nisshinbo Industries, Inc. Hydrophilic tetramethylxylylenecarbodiimide
US5912290A (en) * 1996-02-06 1999-06-15 Nisshinbo Industries, Inc. Hydrolysis stabilizer for ester group-containing resin
US5925409A (en) * 1997-08-27 1999-07-20 Reichhold, Inc. Resins for lining surfaces
US5958516A (en) * 1994-08-11 1999-09-28 Nisshinbo Industries, Inc. Method for surface treating reinforcing material with aqueous carbodiimide containing composition
US6017742A (en) * 1994-07-20 2000-01-25 Nisshinbo Industries, Inc. Immobilization of biologically active substances on a carrier containing a carbodiimide group-containing polymer
US6121406A (en) * 1998-04-20 2000-09-19 Nisshinbo Industries, Inc. Mixture of hydrophilic dicyclohexylmethanecarbodiimide
US6204342B1 (en) 1997-08-27 2001-03-20 Reichhold Chemicals Thickening active H-containing resin with polycarbodiimide
US20030119954A1 (en) * 2001-12-13 2003-06-26 Brown Ward Thomas Crosslinkable composition
CN1120191C (en) * 1998-07-01 2003-09-03 巴斯福公司 Polycarbided diimine polymer and its use as inter-layer of adhesive layer in automobile paint
US6692802B1 (en) 1997-08-27 2004-02-17 Reichhold, Inc. Resins for lining surfaces
US20040158021A1 (en) * 2003-02-10 2004-08-12 Nitto Denko Corporation Polycarbodiimide having high index of refraction and production method thereof
US20040157992A1 (en) * 2003-02-04 2004-08-12 Nitto Denko Corporation Resin for the encapsulation of photosemiconductor element, photosemiconductor device comprising encapsulated optical semiconductor element, and process for producing the device
US20050142379A1 (en) * 2003-12-26 2005-06-30 Nitto Denko Corporation Electroluminescence device, planar light source and display using the same
US20060098066A1 (en) * 2003-11-12 2006-05-11 Bauer Richard D Inkjet ink, ink set and method of printing
US9957394B2 (en) 2016-09-07 2018-05-01 Ppg Industries Ohio, Inc. Methods for preparing powder coating compositions
US10058502B2 (en) 2015-12-31 2018-08-28 L'oreal Nail polish compositions

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DE4318979A1 (en) * 1993-06-08 1994-12-15 Basf Ag Carbodiimides and / or oligomeric polycarbodiimides based on 1,3-bis (1-methyl-1-isocyanatoethyl) benzene, a process for their preparation and their use as a hydrolysis stabilizer
DE69827547T2 (en) * 1997-05-19 2005-11-24 Nisshinbo Industries, Inc. Powder coating curing agent, powder coating composition containing this curing agent and powder coating film
EP0969029B1 (en) * 1998-06-05 2003-11-26 Basf Corporation Novel polycarbodiimide polymers and their use as adhesive intermediate layers in automotive coatings
JP4977034B2 (en) 2005-11-28 2012-07-18 サカタインクス株式会社 Liquid developer
JP6055353B2 (en) * 2013-03-28 2016-12-27 日清紡ケミカル株式会社 Ester resin composition, method for producing ester resin composition, and molded article using ester resin
WO2024083487A1 (en) 2022-10-18 2024-04-25 Sabic Global Technologies B.V. Method of preparing a hydrostable thermoplastic composition
WO2024083483A1 (en) 2022-10-18 2024-04-25 Sabic Global Technologies B.V. Hydrostable thermoplastic composition

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EP0582983B1 (en) 1996-10-09

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